Production of halogen-substituted, unsaturated alcohols



United States Patent 3,324,187 PRODUCTEON OF HALOGEN-SUBSTITUTED,UNSATURATED ALCOHOLS Morton H. Litt, Morristown, and George J. Schmitt,

Madison, N.J., assignors to Allied Chemical Corporation, New York, N.Y.,a corporation of New York No Drawing. Filed Dec. 5, 1961, Ser. No.157,270 10 Claims. (Cl. 260-633) The present invention relates to newand useful halogen-substituted, unsaturated alcohols and to a processfor their manufacture. More particularly, the invention relates to newand useful, fluorine-substituted, olefinic alcohols and to a process forthe preparation of said alcohols.

It has been proposed to prepare unsaturated, fluorinated alcohols bytreatment of hexafluoroacetone with acetylene magnesium halides.Processes of this type, commonly known in the art as Grignard reactions,are applicable for the preparation of a variety of halogenated,unsaturated alcohols by interaction of halogenated ketones or aldehydeswith organomagnesium compounds. These processes are undesirable from acommercial standpoint, however, in view of the necessary utilization ofrelatively expensive Grignard reagents.

We have now discovered that fluorine-substituted, olefinic alcohols maybe economically prepared in high yield by intimately admixing undersubstantially anhydrous conditions a fluorine-substituted,perhalogenated acetone with an tit-olefinic compound having at leastthree carbon atoms in the olefinic chain.

Preferred perhalogenated acetone possess the general formula F C12CCCClzF 1,1,3,3-tetrachloro-1,3-difiuoroacetone t C 1 0 l O F 31,1,1-trit1u0ro-3,3,3-trichloroacetone Preferred tit-olefinic compoundspossess formula the general 3,324,187 Patented June 6, 1957 wherein R isa member selected from the group consisting of alkyl, cycloalkyl, aryl,aralkyl, alkoxy and aryloxy and R and R are like or unlike membersselected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl,:aralkyl, alkoxy, aryloxy, halogen, amido, acyl, carboalkoxy, vinyl andallyl.

Specifically, R may be methyl, ethyl, propyl, butyl, cyclohexyl, phenyl,naphthyl, benzyl, methoxy, ethoxy, propoxy and phenoxy. R and R may behydrogen, methyl, ethyl, propyl, butyl, phenyl, naphthyl, benzyl,cyclohexyl, methoxy, ethoxy, propoxy, but-oxy, phenoxy, chlorine,bromine, fluorine, iodine, acetamido, acetyl, propionyl, carbomethoxy,carboethoxy, carbopropoxy, carbobutoxy, vinyl, and allyl. Theseradicals, however, are merely illustrative.

Among the aforesaid substituent groups, those derived from hydrocarbonmolecules may, in themselves, possess a variety of addtional secondarysubstituents. The secondary substituents may be any one of thesubstituent groups, R R and R defined hereinabove. In addition, othersecondary substituents may be present provided that the substituents donot appear nearer to the terminal olefinic linkage than on a carbon atomin a position beta to said linkage. Members of this last-named class ofsubstituents may be selected from the group consisting of amino,hydroxy, dialkylamino, diarylamino, dicycloalkyl'amino anddiaralkylamino.

Alternatively, a-olefinic compounds of the above formula wherein R ishydrogen or acyloxy (e.g. acetoxy) may be employed. In this instance, Rand R may be like or unlike members selected from the group consistingof hydrogen, alkyl, cycloalkyl, aryl, aralkyl land alkoxy. In addition,R and R may possess the secondary substituents described above.

Illustrative examples of a-olefinic compounds suitable for the processof our invention are given below,

CH CH=CHz propylene CHsCHzCH=OHz l-butene O=CHQ isobutylene CH (CH)1CH=CHz l-decene on2=on-on2on2-crr=cm 1,5-hexadiene 0 i C H3 0 H3- 0 0Hz 2-aeet oxypropene C H2: C C H2 0 l 2-methyl-3-chloropropeneabenzylpropene a-methylstyrene CH3 CH2 limonene H3 0 Hz2-cyclohexylpropene -isopropenylmethylbenzoate C HEN O z CH3CH2C=CII12-nitron1cthyl-1-butene CH3 CII3CH2C=CH2 2-methoxy-1-butene Although wedo not wish to be bound by any particular theory, it appears that analkene compound possessing a terminal olefinic linkage is necessary fora facile reaction rate in our process. The process may be bestillustrated by reference to Equation 1, wherein the formation of thefluorine-substituted olefinic alcohols features a migration andretention of the olefinic linkage originally present in the molecule.

In those alkene compounds which possess two terminal olefinic linkages,it is possible to interact perhalogenated acetones therewith to producea dihydric, fluorine-substituted olefinic alcohol. Such a process may beillustrated by Equation 3, wherein 1,5-hexadiene is employed as Z theolefinic compound and X is a halogen as defined above.

The process of this invention must be conducted under substantiallyanhydrous conditions. The presence of water or any electron-donatingspecies, such as ammonia or amines or alcohols, will tend to interactwith an equivalent number of perhalogenated acetone molecules to formcomplexes with the molecules, rendering said molecules inactive.

The most convenient manner for excluding extraneous inhibitors is byadmixing the perhalogenated actone with concentrated sulfuric acid orother suitable drying agent, and distilling the acetone therefrom, underreduced pressures, if necessary. However, any procedure readilyavailable to those skilled in the art may be employed.

In order to produce a monohydric fluorine-substituted olefinic alcoholfrom a monoolefinic compound which will not form a dihydric alcohol, amol ratio of perhalogenated acetone to monoolefinic compound of at least1:1 is preferred. However, an excess of either reactant may be useddepending on the value of the reactant and its ease of separation. Theproduction of a dihydric olefinic alcohol from a monoolefinic compoundcapable of producing the same requires that the ratio of perhalogenatedacetone to monoolefinic compound be at least 2:1. The degree of excessin either instance is not critical and may be as large as economicconsiderations will permit. Preferably, however, not more than about 3times the theoretical mol ratio is used in either case. Hence, forproduction of a monohydric alcohol where formation of no dihydricalcohol is possible, a mol ratio of perhalogenated acetone tomonoolefinic compound ranging from 1:1 to about 3:1 is generallyemployed. For production of a dihydric alcohol from a monoolefiniccompound capable of forming the same, the mol ratio may range from 2:1to about 6: 1. In those instances where it is desired to produce amonohydric alcohol from a diolefinic compound or a monoolefinic compoundwhich will form a dihydric alcohol, the converse ratio may be employed,i.e., a mol ratio of perhalogenated acetone to olefinic compound lessthan 1: 1, the ratio being dependent upon the relative reactivity of theolefinic groups but usually ranging from about 0.2 to 0.921. Forproduction of a dihydric alcohol from a diolefinic compound, a mol ratioof perhalogenated acetone to diolefinic compound ranging from 2:1 toabout 6:1 is generally used.

Care must be exercised when employing tat-olefinic compounds containinghydroxy, amino and the like groups in the olefinic molecule inasmuch asthe hydroxy and amino moiety of such olefinic compounds may function toinactivate a portion of the perhalogenated acetone present in thereaction mixture. The undesirable reduction in yield predicated by saiddeactivation may be circumvented by utilization of an excess of theperhalogenated acetone, and, at termination of the process, by utilizinga quantity of mineral acid to rupture the complexes thus formed. Theunreacted, perhalogenated acetone may then be separated from thecondensation products in the reaction mixture.

Although the preferred temperature range for the reaction is from about20 to 100 C., temperatures as low as C. and as high as 250 C. areapplicable.

In the preferred mode of operation, the process is performed in theabsence of any solvent, but, if control of reaction rate is desired,inert organic solvents which will not appreciably inactivate thecarbonyl group of the perhalogenated acetones may 'be used. Suitablesolvents include aromatic and aliphatic hydrocarbons such as toluene,benzene, xylene, pentane, hexane, and petroleum ether, as well as etherssuch as tetrahydrofuran and nitriles such as acetonitrile. The presenceof such solvents acts to slow down the reaction rate of the process byvirtue of dilution and complex formation of the solvent with theperhalogenated acetone.

The dihydric, fluorine-substituted, olefinic alcohols of our inventionare admirably suitable for the production of epoxy resins as describedin Example hereinbelow. The resins may be used as adhesives, asindicated by their high resistance to abrasion, their flexibility, andtheir resistance to a variety of chemical solvents. Preferred dihydricalcohols may be represented by the following general formula wherein Ris a member selected from the group consisting of alkyl, cycloalkyl,aryl, aralkyl, alkoxy and aryloxy, R is a member selected from the groupconsisting of hydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkoxy,halogen, amido, acyl, carboalkoxy, vinyl and allyl, X is a memberselected from the group consisting of chlorine and fluorine, the totalnumber of chlorine represented by X ranging from 0 to 4, m is an integerranging from 0 to 1, n is an integer ranging from 0 to 20 and p is aninteger ranging from 0 to 1.

Alternatively, R may be hydrogen or acyloxy, in which case R is a memberselected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl,aralkyl and alkoxy.

The monohydric alcohols of the invention are useful as plasticizers forresinous compositions. These alcohols may be esterified and the highlyhalogenated, inert esters produced therefrom employed for thestabilization of resinous materials against the decompositional effectsof heat.

The following specific examples will further illustrate the invention.In the examples, parts are by weight and temperatures are in degreescentigrade.

Example 1 l CH3 C F3 The product was obtained in a yield of 100% oftheorectical and possessed a refractive index, n -=1.3503, and thefollowing elemental analysis:

Theoretical: C, 37.84%; H, 3.62%. Found: C, 37.64%; H, 3.69%.

Example 2 The procedure of Example 1 was repeated utilizing 14.0 partsof isobutylene and 83.0 parts of hexafluoroacetone. After standing for12 hours at 25 in a dry, sealed ampule, the ampule was opened. A solidproduct was obtained which was recrystallized from chloroform. Theproduct, having the following structural formula, melted at 146447".

The product exhibited an infrared spectrum wherein the presence ofolefinic double bonds was indicated by absorption at 10.35 microns,carbon-hydroxy absorption at 3.0 microns and carbon-fluorine absorptionat 8.1-8.4 microns.

Example 3 l-butene (13.4 parts) was admixed with hexafluoroacetone (21.5parts) in the manner described in Example 1. The ampule was permitted tostand at room temperature for 12 hours, and was then cooled to 0 andopened. A liquid residue was obtained (15 parts) which distilled at 65.566.5 under mm. Hg pressure to yield a clear distillate of1,1,1-trifluoro-2 hydroxy-2-trifluoromethyl-4- hexene possessing arefractive index, n 1.3475, and the following structural formula Theproduct had the following elemental analysis:

Theoretical: C, 37.84%; H, 3.62%. Found: C, 37.87%; H, 4.10%.

Example 4 Propylene (14 parts) was distilled under vacuum (10 mm. Hgpressure) into a stainless steel autoclave under anhydrous conditions.In a similar manner, hexafiuoroacetone (60 parts) was added, and thebomb was sealed and heated at for 12 hours. Upon cooling, the bomb wasopened and the liquid reaction mixture was distilled at 42.8 43.0 under68 mm. Hg pressure to produce 5.3 parts of1,1,1-trifluoro-2-hydroxy-2-trifiuoromethyl-4-pentene of the followingstructural formula Example 5 In a manner similar to that described inExample 1, carefully dried 2-acetoxypropene'(10.1 parts) was admixedwith hexafluoroacetone (11.4 parts), sealed in an ampule, and heatedfirst at 25 for 56 hours, then at 60 for 15 hours and finally at 100 for38 hours. The ampule was cooled to 0 in an ice bath and opened. Theliquid reaction mixture was washed with water, and then dried overmagnesium sulfate. The compound which was isolated,1,1,1-trifluoro-2-hydroxy-2-trifiuoromethyl- 4-acetoxy-4-pentene,possessed a refractive index.

n =L3332 and the following structural formula The infrared spectrum ofthe product had absorption bands at 3.31 and 5.99 microns indicative ofolefinic bonds, a band at 2.95 microns indicating the presence of ahydroxy group, a band at 8 microns indicative of the presence of acarbon-fluorine bond and bands at 5.83 and 8.0 microns indicating thepresence of a carbonyl group.

Example 6 In a manner similar to that described in Example 1,a-methylstyrene 11.8 parts) was admixed with1,3-dichloro-l,1,3,34etrafluoroacetone' (19.9 parts) and permitted tostand for 60 hours at 60. The viscous reaction mixture thereby obtainedwas distilled at 8689 under 0.6 mm. Hg pressure to yield1,l-difiuoro-l-chloro-Z-difiuorochloromethyl-2-hydroxy-4-phenyl-4pentenewhich possessed a refractive index, n -=1.4925, and the followingstructural formula In addition, the infrared spectrum of the productpossessed absorption bands at 6.25 and 6.35 microns indicative of abenzenoid nucleus, bands at 12.9 and 14.3 indicating a mono-substitutedbenzenoid group, a band at 2.84 microns indicative of a hydroxy group, aband from 8.4 to 8.8 microns indicating a carbon-fluorine bond, a bandat 6.12 microns indicative of an olefinic group and bands at 3.45 and6.9 microns indicative of the presence of a methylene group.

Example 7 The process of Example 6 was repeated employing 9.9 parts ofa-methylstyrene and 44.7 parts of 1,3-dichloro-1,1,3,3-tetrafiuoroacetone. The product had the following structuralformula The product exhibited the following elemental analysis:

Theoretical: C, 34.9%; H, 1.94%; Cl, 27.5%. Found: C, 35.19%; H, 2.50%;Cl, 27.0%.

In addition, the product exhibited infrared spectrum showing absorptionbands at 6.33 and 6.68 microns indicative of the presence of a benzenoidnucleus, bands at 13.05 and 14.35 microns indicating a mono substitutedbenzenoid nucleus, asborption bands from 8.4 to 8.7 microns indicativeof a carbon-fluorine bond, a band at 6.09 microns indicative of anolefinic linkage and a band at 2.99 microns indicative of the presenceof a hydroxy group.

Example 8 In a manner similar to that described in Example 1,1,5-hexadiene (8.2 parts) was admixed with 1,3-dichloro-1,1,3,3-tetrafiuoroacetone (19.9 parts) and maintained in a sealedampule for 24 hours at 100. The mixture was then distilled on a spinningband column at 4344 under 0.4 mm. Hg pressure to yield1,l-difluoro-l-chloro-Z-hydroxy-2-difiuorochloromethyl-4,7-octadiene(25.3 parts) of the following structural formula The product possessed arefractive index, n =1.4395, and had the following elemental analysis:

Theoretical: C, 38.4%; H, 3.58%. Found: C, 38.01%; H, 3.78%.

Infrared spectrum of the product showed the presence of an absorptionband at 2.85 microns indicative of a hydroxy group, a band from 8.4 to8.8 microns indicating a carbon-fluorine bond and a band at 3.25 and 6.1microns indicative of an olefinic linkage.

Example 9 The procedure of Example 8 was repeated with 4.1 parts of1,5-hexadiene and 29.9 parts of 1,3-dichloro-l,1,3,3-tetrafluoroacetone. A yield of 34.3 parts of 1,1,53,8-

tetra (difiuorochloromethyl)-1,8-dihydroxy-3,5 octadiene of thefollowing structural formula was obtained The product possessed arefractive index, m 1.4574, and had the following elemental analysis:

Theoretical: C, 30.00%; H, 2.08%; F, 29.4%. Found: C, 30.45%; H, 2.20%;F, 28.56%.

Infrared spectrum of the product showed a hydroxy band at a wave lengthof 2.83 microns, an absorption band at 8.48.75 microns indicative of acarbon-fluorine bond, an absorption band at 3.4 and 6.94 micronsindicating the presence of a methylene group and an absorption band at3.29 and 6.01 microns indicating the presence of olefinic' groups.

Example 10.Preparation of epoxy resin The dihydric alcohol produced byExample 2 (19.4 parts) was admixed in a resin pot with epichlorohydrin(46,25 parts) and distilled water (0.5 part). The resin pot was equippedwith a condenser, a thermowell, a mechanical stirrer and a reagent feedopening. The reaction mixture was agitated and heated at 60 for 30minutes, at the end of which 1.0 part of sodium hydroxide was addedthereto. The temperature was increased to 75 and maintained at thattemperature for about 15 minutes, then dropped to 60 at which timeadditional sodium hydroxide (1.0 part) was added. This procedure wasrepeated two more times until a total of about 4.2 parts of sodiumhydroxide had been added to the reaction mixture. The temperature ofsaid mixture was then raised to 95 and maintained at that temperaturefor one hour. At the end of this itme, unreacted epichlorohydrin andwater were removed from the reaction mixture by distillation at 150under mm. Hg pressure, and the residue was permitted to cool to about25. Acetone (25 parts) was then added to the residue and insoluble saltswere removed from the resulting mixture by filtration. The filtrate wascollected and acetone was removed therefrom by distillation at 120 under90 mm. Hg pressure. A clear, waterwhite liquid was obtained in 60% yieldof theoretical based on the monomer added to the initial reactionmixture. The material was an epoxy resin possessing an epoxideequivalent of 298.

This resin was readily transformed into a film by admixing the resin (5parts) with diethylene triamine (0.35 part) and acetone (20 parts). Acured film was prepared on a bonderized steel panel by heating the abovemixture at for one hour. The product obtained possessed the filmproperties illustrated in Table I.

TABLE I.PHYSICAL PROPERTIES Mandrel Test 1 l Tape Test 2 Rocker Hardness3 Passed Passed 50 CHEMICAL PROPERTIES 5%NaOH Water Toluene Acetone NoEffect N0 Effect I No Effect i No Effect 1 ASTM D522-41.

2 A V-shaped cut was made in the Him, and a strip of cellophane tape waspressed down on the film and abruptly ripped away to See if it removedany of the film.

@ Organic Coating Technology, J. Wiley & Sons, page 642, 1959.

While the above describes the preferred embodiments of this invention,it will be understood that departures may be made therefrom within thescope of the appended claims.

9 We claim: 1. A fluorine-substituted, olefinic alcohol having thegeneral formula wherein R is a member selected from the group consistingof alkyl containing from 1 to 7 carbon atoms, cyclohexyl, phenyl,naphthyl, alkoxy containing from 1 to 4 carbon atoms,methylcyclohexenyl, carbomethoxyphenyl and nitromethyl, R and R aremembers selected from the group consisting of hydrogen, alkyl containingfrom 1 to 7 carbon atoms, benzyl and halogen and X is a member selectedfrom the group cosisting of chlorine and fluorine, the total number ofchlorine atoms represented by X ranging from to 4.

2. A fluorine-substituted, olefinic alcohol having the general formulawherein R is a member selected from the group consisting of hydrogen andacetoxy, R and R are members selected from the group consisting ofhydrogen, alkyl containing 1 to 7 carbon atoms and allyl and X is amember selected from the group consisting of chlorine and fluorine, thetotal number of chlorine atoms represented by X ranging from 0 to 4.

3. A fluorine-substituted, olefinic alcohol having the general formulawherein R is a member selected from the group consisting of hydrogen,alkyl containing 1 to 7 carbon atoms, phenyl and naphthyl, X is a memberselected from the group consisting of chlorine and fluorine, the totalnumber of chlorine atoms represented by X in each a GEE-(l3- groupranging from 0 to 4, m is an integer ranging from O to 1, n is aninteger ranging from 0 to 20 and p is an integer ranging from 0 to 1.

4. A fluorine-substituted, olefinic alcohol having the general formulaof claim 3 wherein m, n and p are 0.

5. A fluorine-substituted, olefinic alcohol having the 5 general formulaof claim 3 wherein m and p are 1.

6. The fluorine-substituted, olefinic alcohol having the formula 7. Thefluorine-substituted, olefinic alcohol having the formula 8. Thefluorine-substituted, olefinic alcohol having the formula 9. Thefluorine-substituted, olefinic alcohol having the formula 11). Thefluorine-substituted, olefinic alcohol having the formula OTHERREFERENCES Knunyants et al.: Chem. Abstracts, vol. 54, p. 20872g (1960).

Young et al.: J. Am. Chem. Soc., vol. 81, pp. 490-3 (1959).

5 LEON ZITVER, Primary Examiner.

LOUISE P. QUAST, Examiner.

A. L. LIBERMAN, T. G. DILLAHUNTY,

Assistant Examiners.

1. A FLUORINE-SBUSTITUTED, OLEFINIC ALCOHOL HAVING THE GENERAL FORMULA3. A FLUORINE-SUBSTITUTED, OLEFINIC ALCHOL HAVING THE GENERAL FORMULA